Les explorations scientifiques menées depuis une quarantaine d’années ont permis d'identifier la diversité et la complexité des processus géologiques et géochimiques conduisant à la concentration des métaux dans les grands fonds océaniques. Les dépôts métallifères riches en hydroxydes de Fer et de Manganèse, tels que les encroûtements hydrogénétiques et hydrothermaux et les nodules polymétalliques, présentent des enrichissements variés en éléments d'intérêts économiques tels que le Ni, Cu, Co, Te, Pt et les Terres Rares. Bien que la minéralogie et la géochimie de ces dépôts aient été largement étudiées dans la littérature, les sources de métaux restent encore mal déterminées. Par conséquent, comprendre la géochimie de ces dépôts implique d’une part, de connaître les processus participant à leur genèse, et d’autre part d’avoir de meilleures connaissances sur les sources impliquées (par ex. flux continental et hydrothermal) et leur importance dans les grands cycles biogéochimiques des métaux dans les océans. Afin d’apporter de nouveaux éléments de réponse, notre approche a consisté à utiliser les compositions isotopiques des métaux comme traceurs biogéochimiques. Ce projet est structuré autour de deux hypothèses, (1) le développement et l’utilisation d’un nouveau outil géochimique que sont les isotopes du Ni pour tracer les sources et les processus d’enrichissements en métaux dans les dépôts métallifères océaniques ; (2) la combinaison de plusieurs systèmes isotopiques tels que Fe, Pb, Cu et Zn (et Ni) dans les encroûtements de fer-manganèse comme proxy de la composition isotopique de l’eau de mer profonde. Après avoir développé une méthode d’analyse des isotopes du Ni par MC-ICP-MS et estimé la variabilité isotopique du Ni dans les systèmes naturels par la caractérisation des grands réservoirs terrestres, nous avons évalué expérimentalement le fractionnementisotopique du Ni lors de son adsorption sur les oxyhydroxydes de Fe et Mn comme analogue à ce qui pourrait se produire dans les dépôts de Fe-Mn naturels. Les résultats indiquent que lors de l’adsorption du Ni, la phase solide est enrichie en isotopes légers par rapport à la solution avec des facteurs de fractionnement (Δ60/58Nimin/sol) variant de -1 ‰ pour la birnessite, -0.9 ‰ pour la goethite et -0.4 ‰ pour la ferrihydrite. A partir de ces résultats et d’autres études récentes, nous avons pu appuyer l’hypothèse selon laquelle d’un point de vue global la variabilité isotopique du Ni dans les dépôts métallifères océaniques riches en Fe et Mn s’explique par des processus d’enrichissement et de formation lors de l’incorporation des métaux dans les phases minérales de Fe et Mn plutôt que par des variations des compositions isotopiques des sources. Ainsi les encroûtements hydrogénétiques formés lentement à partir de l’eau de mer ne montrent pas de fractionnement isotopique du Ni, tandis que les dépôts hydrothermaux formés par des processus rapides liés aux apports hydrothermaux montrent des fractionnements du Ni plus importants. Puis, afin d’évaluer la possibilité d’utiliser les signatures isotopiques du Ni comme nouveaux traceurs paléocéanographiques, nous avons mené une étude comparative sur des encroûtements collectés dans le Pacifique Nord (proche de Hawaii) et le Pacifique Sud (proche de Tahiti). Dans ce contexte, les ncroûtements de fer-manganèse formés par précipitation très lente de l’ordre de quelques mm/Ma entre 1500 et 3000 m de profondeur, fournissent un enregistrement de plusieurs millions d’années des métaux dissous dans l’eau de mer. Après avoir réalisé une étude minéralogique et géochimique (éléments majeurs et traces) et calibré les taux de croissance des encroûtements, nous avons mesuré pour la première fois les compositions isotopiques du Ni, Fe, Zn, Cu et Pb sur la même série temporelle. / Scientific explorations implemented for around forty years allow to identifying the diversity and the complexity of geological and geochemical processes conducting to metals concentration on the deep seafloor. Fe- and Mn-rich metalliferous deposits such as hydrogenetic and hydrothermal ferromanganese (Fe-Mn) crusts and polymetallic nodules, present various enrichment in elements of economic interests like Ni, Cu, Co, Te, Pt and Rare Earth Elements. Although the mineralogy and geochemistry of these deposits have been largely studied in the literature, metal sources remain poorly determined. Accordingly, understanding the geochemistry of these deposits implies to know which processes are involved in their formation but also to have a better knowledge of the sources (e.g. the continental and hydrothermal fluxes) and their importance in the global oceanic metal biogeochemical cycles. In order to fill this gap, our approach consisted in using metal stable isotope compositions as biogeochemical tracers. This project is organized around two hypotheses, (1) development and utilization of a new geochemical tool, namely Ni isotopes, for tracing metal enrichment sources and processes in oceanic metalliferous deposits; (2) combination of several isotope systematics such as Fe, Pb, Cu, Zn (and Ni) in Fe-Mn crusts as proxies of the deep seawater isotope composition. Upon developing an analytical method for measuring Ni isotopes by MC-ICP-MS and estimating the Ni isotopes variability in natural systems through the characterization of terrestrial reservoirs, we experimentally evaluated Ni isotope fractionation during adsorption on Fe- and Mn-oxyhydroxides since similar processes may potentially occur in natural Fe-Mn deposits. Results indicate that after Ni adsorption, the solid phase is enriched in light Ni isotopes relatively to the solution with fractionation factors (Δ60/58Nimin/sol) varying from -1 ‰ for birnessite, -0.9 ‰ for goethite and -0.4 ‰ for ferrihydrite. These results, and other recent studies, strengthen our hypothesis according to which Ni isotopes variability in Fe- and Mn-rich metalliferous deposits can be explained by enrichment and formation processes during metal incorporation in Fe and Mn mineral phases rather than variations in the isotopic composition of the sources. Thus, hydrogenetic Fe-Mn crusts formed slowly from seawater dissolved metals do not show significant Ni isotope fractionation, whereas hydrothermal deposits formed by relatively rapid processes as a result of hydrothermal inputs exhibit important Ni isotope fractionation.

Submitted by Silvana Teresinha Dornelles Studzinski (sstudzinski) on 2016-09-21T15:45:10Z No. of bitstreams: 1 Rodrigo do Monte Guerra_.pdf: 12842392 bytes, checksum: b6db9de51a65dd59c144edac22f16cab (MD5) / Made available in DSpace on 2016-09-21T15:45:10Z (GMT). No. of bitstreams: 1 Rodrigo do Monte Guerra_.pdf: 12842392 bytes, checksum: b6db9de51a65dd59c144edac22f16cab (MD5) Previous issue date: 2016-01-19 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Milton Valente / O final do período Cretáceo é caracterizado por uma gradual transição climática de escala global, fator que modificou a composição das assembleias de nanofósseis calcários e por conta disso vem causando problemas nas interpretações bioestratigráficas entre diferentes faixas latitudinais. Apesar de possuir alguns estudos realizados principalmente entre as décadas de 1980 e 1990, existe uma carência na avaliação do Atlântico Sul como um todo. Desta forma, este estudo objetiva descrever as assembleias de nanofósseis calcários comuns em cada faixa latitudinal e testar o sincronismo dos principais bioeventos. Foram analisadas 649 amostras provenientes de doze seções testemunhadas pelos projetos Deep Sea Drilling Project (DSDP) e Ocean Drilling Program (ODP) nas proximidades da margem brasileira e africana, além de um afloramento na Península Antártica. O estudo taxonômico possibilitou a identificação de 197 espécies de nanofósseis calcários do Campaniano e Maastrichtiano. Através do uso conjunto da bioestratigrafia e magnetoestratigrafia, foram reconhecidos diacronismos em eventos de primeira e última ocorrência de espécies do Campaniano superior e Maastrichtiano superior. Este diacronismo está relacionado a migrações de espécies entre baixas e médias latitudes, decorrentes de mudanças na circulação oceânica e temperatura das águas superficiais. Com base na variação latitudinal das assembleias de nanofósseis calcários, um detalhado estudo bioestratigráfico possibilitou a divisão de três zoneamentos para o Atlântico Sul (baixas, médias e altas latitudes). Além disso, foram definidos os padrões de distribuição de diversas espécies, mostrando uma clara divisão paleobiogeográfica entre espécies que ocorrem somente em latitudes altas e outras limitadas a latitudes médias a baixas. Este padrão possivelmente foi controlado por variações na temperatura das massas de água superficiais. Outras espécies possuem sua distribuição variada em todas as faixas latitudinais, tendo sua distribuição relacionada provavelmente à disponibilidade de nutrientes. / The Late Cretaceous period is characterized by global climatic transition that influenced calcareous nannofossil assemblages posing a challenge for biostratigraphic interpretation between different latitudinal degrees. There are a few studies on South Atlantic calcareous nannofossils from 1980 and 1990 decades, but none of them evaluate the South Atlantic as a whole. Therefore, this study aims to describe the calcareous nannofossils assemblages in each latitudinal zone and test the bioevents synchroneity. It were selected 649 samples from twelve cored sections coming from DSDP (Deep Sea Drilling Project) e ODP (Ocean Drilling Program) close to the Brazilian and African margins, in addition to an outcrop in the Antarctic Peninsula. The taxonomic study allowed the identification of 197 calcareous nannofossils species from the Campanian and Maastrichtian. Using the correlation between the biostratigraphical data and magnetostratigraphy, it was possible to identify diachronism in some bioevents of first and last occurrences during the late Campanian and late Maastrichtian. This diachronism is related to species migration between low and mid-latitudes, due to changes in the ocean circulation and surface water temperature. Based on the latitudinal variation in the calcareous nannofossils assemblages, a detailed biostratigraphic study enabled the South Atlantic division in three zonations (low, medium and high-latitudes). We also defined the distribution pattern of some species, indicating a clear paleobiogeographical division between high latitude species and some species limited to low and mid-latitudes. This pattern was possibly controlled by surface water temperature variation. Other species have a wide distribution across the latitudes probably related to nutrient availability.

Methane derived authigenic carbonate (MDAC) precipitation occurs within marine sediments as a byproduct of the microbial anaerobic oxidation of methane (AOM). While these carbonates form in chemical and isotopic equilibrium with the fluids from which they precipitate, burial diagenesis and recrystallization can overprint these signals. Plane polarized light (PPL) and cathodoluminescent (CL) petrography have allowed for detailed characterization of carbonate phases and their subsequent alteration. Modern MDACs sampled offshore in northern Cascadia (n =33) are compared with paleoseep carbonates (n =13) uplifted on the Olympic Peninsula in order to elucidate primary vs. secondary signals, with relevance to interpretations of the carbonate record. The modern offshore environment (S. Hydrate Ridge and Barkley Canyon) is dominated by metastable acicular and microcrystalline aragonite and hi-Mg calcite (HMC) that with time will recrystallize to low-Mg calcite (LMC). The diagenetic progression is accompanied by a decrease in Mg/Ca and Sr/Ca ratios while variation in Ba/Ca depends upon the Ba-concentration of fluids that spur recrystallization. CL images discern primary carbonates with high Mn/Ca from secondary phases that reflect the Mn- enrichment that characterizes deep sourced fluids venting at Barkley Canyon. Methane along the Cascadia continental margin is mainly of biogenic origin, where reported strontium isotopic values reflect a mixture of seawater with fluids modified by reactions with the incoming Juan de Fuca plate. In contrast, the Sr-isotopic composition of carbonates and fluids from Integrated Ocean Drilling Program (IODP) Site U1329 and nearby Barkley Canyon point to a distinct endmember (lowest ⁸⁷Sr/⁸⁶Sr = 0.70539). These carbonates also show elevated Mn/Ca and δ¹⁸O values as low as -12‰, consistent with a deep-source of fluids feeding thermogenic hydrocarbons to the Barkley Canyon seeps. Two paleoseep carbonates sampled from the uplifted Pysht/Sooke Fm. have ⁸⁷Sr/⁸⁶Sr values similar to those of the anomalous Site U1329 and Barkley Canyon carbonates (⁸⁷Sr/⁸⁶Sr = 0.70494 and 0.70511). We postulate that the ⁸⁷Sr-depleted carbonates and pore fluids found at Barkley Canyon represent migration by the same type of deep, exotic fluid as is found in high permeability conglomerate layers down to 190 mbsf at Site U1329, and which fed paleoseeps in the Pysht/Sooke Fm. These exotic fluids likely reflect interaction with the 52-57 Ma igneous Crescent Terrane, which is located down-dip from both Barkley Canyon and Site U1329. This previously unidentified endmember fluid in northern Cascadia may have sourced cold seeps in this margin since at least the late Oligocene. / Graduation date: 2012

Throughout the Holocene, appreciable changes in bathymetry are hypothesized to have resulted in large changes to tidal datums in coastal and estuarine areas. An understanding of tidal change is an important contribution to the knowledge of relative historical sea-level change and future coastal planning. To test this hypothesis, the Advanced Circulation (ADCIRC) model was used, with representative bathymetric grids based on glacial isostatic adjustment models and semi-empirical sea level rise predictions, in order to model the time-varying tidal behavior of the Delaware Bay. Model runs were conducted at various time slices between 10,000 years before present and 300 years into the future on high resolution grids that allowed for inundation moving forward in time. Open boundary tidal forcing was held constant in time to highlight the effect of the changing regional bathymetry. With each change in sea level, the shape of the Delaware Bay was considerably altered, leading to changes in the tides. Resonance and shallow water dissipation appeared to be the primary mechanisms behind these changes. Results showed that tidal ranges have nearly doubled in the upper Delaware Bay over the past 3000 years, while decreasing in the lower bay by 8%. Tidal range change represents a possible correction to past sea level rise estimates from the geologic record. Scenarios incorporating future sea level predictions primarily showed a small decrease in tidal range, potentially impacting future water levels and tidal sediment transport. Trends modeled were consistent with field measurements of relative change over similar time periods. / Graduation date: 2012

Previous studies showed that sea surface salinity (SSS) in the Florida Straits as well as Florida Current transport covaried with changes in North Atlantic climate over the past two millennia. However, little is known about earlier Holocene variability in the Florida Straits. Here, we combine Mg/Ca-paleothermometry and stable oxygen isotope measurements on the planktonic foraminifera Globigerinoides ruber (white variety) from Florida Straits sediment core KNR166-2 JPC 51 (24 degrees 24.70? N, 83 degrees 13.14?W, 198m deep) to reconstruct a high-resolution (~30 yr/sample) early to mid Holocene record of sea surface temperature and delta18OSW (a proxy for SSS) variability. We also measured Ba/Ca ratios in the same shell material as a proxy for riverine input into the Gulf of Mexico over the same time interval. After removing the influence of global delta18OSW change due to continental ice volume variability, we propose that early Holocene SSS enrichments were caused by increased evaporation/precipitation ratios in the Florida Straits associated with periods of reduced solar output, increased ice rafted debris in the North Atlantic and the development of more permanent El Nino-like conditions in the eastern equatorial Pacific. When considered with previous high-resolution reconstructions of early Holocene tropical atmospheric circulation changes, our results provide evidence that solar output variability over the Holocene had a significant impact on the global tropical hydrologic cycle over the last 10,000 years.

This thesis considers the use of two U-series nuclides – 231 Pa and 230 Th – as proxies for studying ocean circulation. A total of six water-column profiles of 231 Pa, 230 Th, and 232 Th have been measured from two regions of the southwestern Indian Ocean: the Madagascar and Mascarene Basins; and the southeastern continental margin of South Africa. Measurement by MC-ICP-MS of 10 litre water samples is possible for samples with as little as 4 and 2 fg of 231 Pa and 230 Th and yields typical uncertainties of 6% and 14% respectively. These profiles show that the scavenging and advection histories of water masses can affect their 231 Pa concentration, with distinct variations superimposed on a general increase in concentration with depth due to reversible scavenging. A 1D particle scavenging model is used to show that sedimentary (231 Paxs /230 Thxs )0 is most representative of the (231 Pa/230 Th) of the bottom most water mass at any one locality, although in turn this water mass (231 Pa/230 Th) will be dependent not only on its advection and scavenging history but also the 231 Pa and 230 Th concentrations of the overlying water masses during advection. Acknowledgment that sedimentary (231 Paxs /230 Thxs )0 is “set” by the bottommost water mass is important for interpretation of scenarios where changes in depth of circulation, as well as circulation strength, may have occurred. A record of sedimentary (231 Paxs /230 Thxs )0 has been recovered from a 6 m Kasten core from the Mascarene Basin covering the past 140 ka, in order to reconstruct flow of AABW into the basin. The (231 Paxs /230 Thxs )0 measured is below the production ration of 0.093 and shows no significant variation. This indicates that (231 Paxs /230 Thxs )0 is sensitive to changes in particle productivity and circulation at this location and that there has been little or no change in either environmental variable over the last full interglacial-glacial cycle. This finding is in contrast to other ocean basins, particularly the North Atlantic, where large changes in circulation are observed.

Les zones à oxygène minimum (OMZs) sont des régions océaniques pratiquement dépourvues d'oxygène. Au cours des derniers milliers d'années, des changements climatiques globaux ont influencé l'intensité et l'extension spatiale de ces zones. Cette thèse propose de reconstruire les concentrations en oxygène dissous des eaux de fond au large de la marge Nord Est du Pacifique pour le Quaternaire supérieur à travers trois méthodes indépendantes, ayant pour dénominateur commun l'enregistrement fossile des foraminifères benthiques. Une première méthode dite micropaléontologique, basée sur l’abondance relative de trois assemblages, est développée dans un premier article. Un second article établit une relation entre l’oxygénation et la porosité de l'espèce Bolivina seminuda, caractérisée par une variation de couverture de pores de la [O$_2$]. Un troisième article est consacré à une méthode morphométrique, basée sur un indice prenant en compte la taille et la circularité des spécimens de chaque échantillon. Chacune de ces méthodes a pu être calibrée grâce aux foraminifères benthiques prélevés dans des sommets de carottes dont la teneur actuelle en oxygène dissous est connue. Ainsi, les estimations quantitatives montrent des valeurs d'oxygène faibles ($\sim$ 0.05 mL.L$^{-1}$) durant les évènements climatiques chauds (évènements de Dansgaard-Oeschger) et plus élevées ($\sim$ 0.5 mL.L$^{-1}$) pendant les évènements froids, pouvant atteindre $\sim$ 1 mL.L$^{-1}$ durant les stades associés aux évènements de Heinrich. Dans un dernier chapitre, ces trois méthodes sont appliquées à l'OMZ de la Mer d'Arabie, et un lien entre oxygénation, mousson indienne, et régime des vents est discuté. / Oxygen minimum zones (OMZs) are areas in the ocean that are almost completely devoid of dissolved oxygen. For several decades, global climate changes are known to be responsible for fluctuations in the intensity and spatial extent of these OMZs. In this thesis, three independent methods were developed for reconstructing the oxygen concentration of OMZ bottom waters during the late Quaternary. All these methods are based on benthic foraminifera preserved in the fossil record. A micropaleontological method is described in a first publication. This approach is based on the relative abundance of three benthic foraminiferal assemblages. A second publication explores the connection between oxygenation and porosity of the benthic foraminiferal species Bolivina seminuda, characterised by a pore surface area that depends on the [O$_2$]. A third article describes a morphometric approach to past oxygen reconstruction based on a semi-automatic method used to calculate an averaged size and roundness index for each sample. Recent benthic foraminifera, recovered from core-top sediments for which the modern bottom water dissolved oxygen content is known, are used to calibrate the three methods. It is found that warm interstadials (corresponding to Dansgaard-Oeschger events) exhibit conditions almost depleted in [O$_2$] ($\sim$ 0.05 mL.L$^{-1}$) while cold stadials show higher values ($\sim$ 0.5 mL.L$^{-1}$) reaching $\sim$ 1 mL.L$^{-1}$ during stadials associated with Heinrich events. In the final chapter, all three methods are successfully applied to the Arabian Sea OMZ, and a link between oxygenation, the indian monsoon, and the local wind regime is discussed.

Indiana University-Purdue University Indianapolis (IUPUI) / Drivers that influence oceanic productivity are not clearly constrained. However, sea level changes during glacial cycles have been proposed as a potential driver for productivity variations observed over warm and cold climate periods. In order to determine this, additional oceanic paleoproductivity data collection is necessary to estimate the ocean’s feedback in response to a dynamic climate. The eastern equatorial Pacific (EEP) is an ideal site for productivity studies due to its high levels of nutrients and deep upwelling. This research examines the phosphorous and barite geochemisty of four EEP sites while also comparing the sites’ glacial and interglacial productivity variations to the geochemistry and productivity results of an independent central equatorial pacific site. Phosphorus and other elemental data were collected from sites 845, 848, 849, and 853 (ODP Leg 138). Using a Ba/Ti and P/Ti proxy (“excess” proxies), distinct productivity variations during glacial and interglacial periods were observed. While the age model for these sites has been estimated, the observed variations more than likely agree with high productivity during glacial periods and lower productivity during interglacial periods. Central equatorial Pacific cores RR0603-03TC and RR0603-03JC (IODP site survey cruise for Proposal 626) have been used as a reference for geochemical concentration parameters, as well as a comparison tool for productivity variations among the central and eastern sites. The central equatorial geochemistry results provided support for sea level changes driving paleoproductivity variations. The similar variation patterns displayed by the EEP’s geochemical data in this research could provide additional support for this hypothesis.

Well-preserved and diverse assemblages of late Campanian-Maastrichtian age (76.5-65.5 Ma) planktic foraminifera from Ocean Drilling Program Sites 1209 and 1210 on Shatsky Rise provide an excellent source of data to better understand the environmental and biotic changes of the end-Cretaceous Period in the tropical Pacific. A thorough taxonomic and biostratigraphic study of planktic foraminifera has revealed significant differences in species ranges when compared to detailed studies from the western North Atlantic and eastern South Atlantic. These observations are attributed to site locations with different ocean current and productivity conditions. During the globally recognized “mid-Maastrichtian Event”, inoceramid clams, rare at Shatsky Rise, dramatically increased (~69.3 Ma) before suddenly going extinct (69.1 Ma). This Inoceramid Acme Event (IAE), occurs during high sedimentation rates (~21.8-m/myr) and is indicated in planktic foraminifera by a 0.50‰ positive shift in δ18O values (~2 °C cooling), a 0.24‰ negative shift in δ13C values of and high species richness. A simultaneous decrease in both the δ18O and δ13C gradients between surface and thermocline dwelling planktic foraminifera indicate the IAE was possibly initiated by an increase in surface productivity due to the upwelling of cooler, nutrient-rich waters. A dissolution event was identified at ~66.1 Ma lasting to the Cretaceous/Paleogene boundary (65.5 Ma) and is characterized by chalky, highly fragmented planktic foraminifera, increased dissolution of larger Globotruncanids, increased small (< 63 μm) planktic foraminifera, large and increasingly abundant benthic foraminifera, a sharp decrease in species richness and increased sedimentation rates (~19.9-m/myr). This event follows a transitional interval at ~66.7 Ma where preservation is highly variable. The dissolution event, reported in previous studies at Shatsky Rise (Caron, 1975; Premoli Silva et al., 2005), is not reported in the North and South Atlantic but may help to explain the high diachroneity in species occurrences between ocean basins. These events may indicate that the calcite carbonate compensation depth (CCD) shoaled to shallower depths than previously reported (Theirstein, 1979) due to changing deep or intermediate water mass sources. Alternatively, the timing the dissolution is approximately coincident with the main pulse of Deccan Trap volcanism on the Indian subcontinent suggesting a possible link through ocean acidification.

No description available.